CN102030878B - Preparing method of oil field demulsifier - Google Patents
Preparing method of oil field demulsifier Download PDFInfo
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- CN102030878B CN102030878B CN2010105484455A CN201010548445A CN102030878B CN 102030878 B CN102030878 B CN 102030878B CN 2010105484455 A CN2010105484455 A CN 2010105484455A CN 201010548445 A CN201010548445 A CN 201010548445A CN 102030878 B CN102030878 B CN 102030878B
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Abstract
The invention discloses a preparing method of an oil field demulsifier. The preparing method adopts ethyleneamine as a raw material, and the oil field demulsifier is prepared by crosslinking modification of the ethyleneamine, ethylene oxide, and propylene epoxide. The method comprises the following steps of: with the ethyleneamine as an initiator, enabling the ethyleneamine to react with propylene oxide and ethylene oxide to prepare an ethyleneamine type polyether demulsifier under the existence of a basic catalyst; carrying out self-crosslinking reaction on the polyether demulsifier A by adopting polycarboxylic acid under the action of a catalyst to prepare a product B; and finally carrying out self-crosslinking reaction on the polyether demulsifier A and the product B in a solvent by adopting toluene diisocynate to prepare a high performance demulsifier as a final product. The demulsifier prepared by the preparing method has the advantages of higher relative molecular weight, favorable dehydration effect and favorable broad spectrum, and can be used for demulsification and dehydration of the crude oil in the oil field. The dehydrated water is clear, and the dosage of the demulsifier is less.
Description
Technical field
The present invention relates to a kind of preparation method of emulsion splitter, the preparation method of the oil field emulsion splitter that the defeated processed of specifically a kind of crude oil collection is used.
Background technology
Often sneak into moisture in the oil production process, will be before Crude Oil Transportation earlier through dehydration, to reduce transportation cost.Free-water in the crude oil is easy to separation removal; Removing emulsified water in the crude oil generally then need add emulsion splitter and carry out; Present domestic use be main with the polyethers emulsion splitter; Such emulsion splitter mostly is to be initiator with the active hydrogen compounds, under the base metal catalysts effect, carries out the anionic ring-opening polymerization reaction with olefin oxide, makes polyoxyethylene poly-oxygen propylene aether class emulsion splitter.The side reaction when preparation higher molecular weight polyethers of this technology is more, and the pfpe molecule amount that makes is lower, and dehydrating effect of emulsion breaker is undesirable, to the wide spectrum bad adaptability of different crude oils oil product.
Summary of the invention
In order to overcome the problem that existing polyethers emulsion splitter exists; The object of the present invention is to provide the preparation method of a kind of oil field emulsion splitter; The present invention is on the basis of preparing polyethylene polyamine type polyethers emulsion splitter; Polyethers emulsion splitter with preparation adopts polycarboxylic acid to carry out the esterification and crosslinking reaction again, and then the product that makes is made with tolylene diisocyanate and the reaction of polyethers emulsion splitter.The emulsion splitter that obtains is the high-performance emulsion splitter that a kind of relative molecular weight is higher, dehydrating effect is desirable, broad spectrum is good.
The objective of the invention is to realize through following technical scheme:
The preparation method of a kind of oil field emulsion splitter is characterized in that this method may further comprise the steps:
At first prepare polyethers emulsion splitter A.With the polyethylene polyamine is initiator, in the presence of basic catalyst, makes polyethylene polyamine type polyethers emulsion splitter A with propylene oxide and ethylene oxide reaction.Catalyzer is one or more mixtures of Monomethylamine, n n dimetylaniline, Trimethylamine 99, Pottasium Hydroxide, sodium hydroxide, and preferred Pottasium Hydroxide for being convenient to use, also can be processed liquid catalyst with catalyst dissolution in water.
Make product B then.Under catalyst action, adopt polycarboxylic acid that polyethers emulsion splitter A is carried out self-crosslinking reaction, make product B.Wherein catalyzer can be Witco 1298 Soft Acid or p-methyl benzenesulfonic acid, preferred p-methyl benzenesulfonic acid.Polycarboxylic acid can be oxalic acid, Succinic Acid or hexanodioic acid, preferred Succinic Acid.
In solvent, adopt tolylene diisocyanate to carry out self-crosslinking reaction polyethers emulsion splitter A and product B at last, make final product high-performance emulsion splitter.Wherein solvent can be toluene, YLENE or kerosene, preferred YLENE.
Preparation polyethers emulsion splitter A concrete steps are following:
Polyethylene polyamine and basic catalyst add in the reactor drum, and heat temperature raising feeds propylene oxide; Controlled temperature is at 115～165 ℃, and pressure maintains below the 0.6MPa, and it is fully reacted; Vacuum 1 hour feeds ethylene oxide again, and controlled temperature is at 115～165 ℃; Pressure maintains below the 0.3MPa, and it is fully reacted, and makes polyethers emulsion splitter A.The wherein wt ratio does; As total amount, polyethylene polyamine accounts for the 0.2-1% of total amount in polyethylene polyamine, propylene oxide and ethylene oxide, and propylene oxide accounts for the 49-79.8% of total amount; Ethylene oxide accounts for the 20-50% of total amount; In total amount, the basic catalyst consumption is 0.2-2%, the preferred Pottasium Hydroxide of basic catalyst.
Preparation product B concrete steps are following:
The polyethers emulsion splitter A of step 1 preparation is added in the reactor drum, add catalyzer, heat temperature raising; Controlled temperature is at 85～115 ℃, and normal pressure adds polycarboxylic acid down, reacts 2 hours; Vacuum 1 hour, process control temp make product B after filtering at 85～115 ℃.The wherein wt ratio does, as total amount, polyethers emulsion splitter A accounts for the 97-99.5% of total amount with polyethers emulsion splitter A and polycarboxylic acid, and polycarboxylic acid accounts for the 0.5-3% of total amount, the preferred Succinic Acid of polycarboxylic acid.In total amount, catalyst levels is 400-4000ppm, the preferred p-methyl benzenesulfonic acid of catalyzer.
Preparation final product high-performance emulsion splitter concrete steps are following:
The polyethers emulsion splitter A of step preparation and the product B of preparation are added in the reactor drum; Add solvent, heat temperature raising, controlled temperature is at 75～85 ℃; Normal pressure drips tolylene diisocyanate down; Process control temp is at 75～85 ℃, drips to finish to keep 75～85 ℃ and it was fully reacted in 1 hour, makes purpose product high-performance emulsion splitter after filtering.The wherein wt ratio does, as total amount, polyethers emulsion splitter A accounts for the 20-40% of total amount with polyethers emulsion splitter A and product B, and product B accounts for the 60-80% of total amount, solvent load be total amount 0.3-3 doubly, the tolylene diisocyanate consumption is the 0.5-6% of total amount.
The at first synthetic polyethylene polyamine type polyethers emulsion splitter of the present invention adopts polycarboxylic acid esterification self-crosslinking then, is dissolved in polyethylene polyamine type polyethers emulsion splitter and the product that adopts polycarboxylic acid esterification self-crosslinking to obtain in the solvent jointly again; Adopt the tolylene diisocyanate crosslinking reaction, obtain the oil field emulsion splitter, the high performance emulsion splitter that makes; Relative molecular weight is higher, and broad spectrum is good, can make the rapid breaking emulsion and dewatering of crude oil; It is clear to deviate from water quality, and dehydrating effect is desirable.
Embodiment
Through specific embodiment the present invention is further specified below, but embodiment is not a limitation of the present invention.
The preparation method of a kind of oil field emulsion splitter may further comprise the steps:
1. polyethers emulsion splitter A's is synthetic: 50 gram polyethylene polyamines and 35 gram Pottasium Hydroxide add in the reactor drum, and heat temperature raising feeds 6750 gram propylene oxides, and controlled temperature is at 115～165 ℃; Pressure maintains below the 0.6MPa, and it is fully reacted, vacuum 1 hour; Feed 3200 gram ethylene oxides again, controlled temperature is at 115～165 ℃, and pressure maintains below the 0.3MPa; And it is fully reacted, and make polyethers emulsion splitter A, subsequent use.
Catalyzer is one or more mixtures of Monomethylamine, n n dimetylaniline, Trimethylamine 99, Pottasium Hydroxide, sodium hydroxide, and the best is a Pottasium Hydroxide, for being convenient to use, also can catalyst dissolution be processed liquid catalyst in water.Present embodiment adopts Pottasium Hydroxide.The wherein wt ratio does, as total amount, polyethylene polyamine accounts for the 0.2-1% of total amount in polyethylene polyamine, propylene oxide and ethylene oxide, and propylene oxide accounts for the 49-79.8% of total amount, and ethylene oxide accounts for the 20-50% of total amount.
The polyethers emulsion splitter A990 gram that 2. will 1. prepare adds in the reactor drum, adds Succinic Acid 10 grams, p-methyl benzenesulfonic acid 1.2 grams, heat temperature raising; Controlled temperature reacted vacuum 1 hour 2 hours at 85～115 ℃; Process control temp makes product B after filtering at 85～115 ℃, and is subsequent use.
Wherein catalyzer can be Witco 1298 Soft Acid or p-methyl benzenesulfonic acid, and present embodiment adopts p-methyl benzenesulfonic acid.Polycarboxylic acid can be oxalic acid, Succinic Acid or hexanodioic acid, and present embodiment adopts Succinic Acid.The wherein wt ratio does, as total amount, polyethers emulsion splitter A accounts for the 97-99.5% of total amount with polyethers emulsion splitter A and polycarboxylic acid, and polycarboxylic acid accounts for the 0.5-3% of total amount.
3. the high-performance emulsion splitter is synthetic:
The polyethers emulsion splitter A300 gram of 1. preparation and product B 700 grams of 2. preparation are added in the reactor drum; Add YLENE 1000 grams; Heat temperature raising, controlled temperature slowly drip tolylene diisocyanate 20 grams at 75～85 ℃; Drip to finish to keep 75～85 ℃ and it was fully reacted in 1 hour, make purpose product high-performance emulsion splitter after filtering.
Solvent is toluene, YLENE or kerosene, and present embodiment adopts YLENE.The wherein wt ratio does, as total amount, polyethers emulsion splitter A accounts for the 20-40% of total amount with polyethers emulsion splitter A and product B, and product B accounts for the 60-80% of total amount, solvent load be total amount 0.3-3 doubly, the tolylene diisocyanate consumption is the 0.5-6% of total amount.
The high performance emulsion splitter that makes, relative molecular weight is higher, and broad spectrum is good, can make the rapid breaking emulsion and dewatering of crude oil, and it is clear to deviate from water quality, and dehydrating effect is desirable.
Claims (1)
1. the preparation method of an oil field emulsion splitter is characterized in that this method may further comprise the steps:
1) with the polyethylene polyamine is initiator, in the presence of basic catalyst, makes polyethylene polyamine type polyethers emulsion splitter A with propylene oxide and ethylene oxide reaction; The wherein wt ratio does; As total amount, polyethylene polyamine accounts for the 0.2-1% of total amount in polyethylene polyamine, propylene oxide and ethylene oxide, and propylene oxide accounts for the 49-79.8% of total amount; Ethylene oxide accounts for the 20-50% of total amount, and the basic catalyst consumption is the 0.2-2% of total amount; Said basic catalyst is one or more mixtures in Monomethylamine, n n dimetylaniline, Trimethylamine 99, Pottasium Hydroxide, the sodium hydroxide;
2) under catalyst action, adopt polycarboxylic acid that polyethers emulsion splitter A is carried out self-crosslinking reaction, obtain product B; The wherein wt ratio does, as total amount, polyethers emulsion splitter A accounts for the 97-99.5% of total amount with polyethers emulsion splitter A and polycarboxylic acid, and polycarboxylic acid accounts for the 0.5-3% of total amount, is 400-4000ppm in the total amount catalyst levels; Catalyzer is Witco 1298 Soft Acid or p-methyl benzenesulfonic acid; Polycarboxylic acid is oxalic acid, Succinic Acid or hexanodioic acid;
3) in solvent, adopt tolylene diisocyanate to carry out self-crosslinking reaction polyethers emulsion splitter A and product B, obtain final product high-performance emulsion splitter; The wherein wt ratio does, as total amount, polyethers emulsion splitter A accounts for the 20-40% of total amount with polyethers emulsion splitter A and product B, and product B accounts for the 60-80% of total amount, solvent load be total amount 0.3-3 doubly, the tolylene diisocyanate consumption is the 0.5-6% of total amount; Solvent is toluene, YLENE or kerosene.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433149B (en) * | 2011-09-06 | 2014-01-15 | 金浦新材料股份有限公司 | Preparation method of modified polyether and solution thereof, and application thereof as diesel oil anti-emulsifying agent |
| CN102807748B (en) * | 2012-08-31 | 2014-01-01 | 句容宁武高新技术发展有限公司 | Preparation method of complex oilfield demulsifier |
| CN102786638B (en) * | 2012-08-31 | 2014-01-29 | 句容宁武高新技术发展有限公司 | Method for preparing viscosity reducer |
| CN103193971B (en) * | 2013-04-16 | 2015-08-26 | 西南石油大学 | The poly(propylene oxide) oil head being initiator with dihydrogenated tallow secondary amine and block polymer demulsifier and preparation method thereof |
| CN103421535B (en) * | 2013-09-02 | 2014-12-10 | 江苏大学 | Step-by-step etherification modified crude oil demulsifier and synthetic method thereof |
| CN103421536A (en) * | 2013-09-02 | 2013-12-04 | 江苏大学 | Epoxy resin chain extension type polyether demulsifying agent and preparation method thereof |
| CN103937536B (en) * | 2013-12-29 | 2016-01-06 | 新疆德蓝股份有限公司 | A kind of new and effective crude oil demulsifier |
| CN104292447A (en) * | 2014-09-18 | 2015-01-21 | 江苏科创石化有限公司 | Coal tar high-efficiency demulsifying agent and preparation method thereof |
| CN105968369A (en) * | 2016-05-26 | 2016-09-28 | 句容宁武高新技术发展有限公司 | Synthetic method for low-temperature efficient demulsifier |
| CN105906796A (en) * | 2016-05-26 | 2016-08-31 | 句容宁武高新技术发展有限公司 | Preparation method of oil-soluble polyether demulsifier |
| CN106335968B (en) * | 2016-10-19 | 2020-05-19 | 中国石油化工股份有限公司 | Demulsifier for high polymer-containing heavy oil sewage and preparation method thereof |
| CN111471482A (en) * | 2020-04-20 | 2020-07-31 | 华东理工大学 | Method for dehydrating high-emulsification sump oil and device adopted by method |
| CN115433352B (en) * | 2022-09-20 | 2023-06-23 | 胜利油田胜利化工有限责任公司 | Modified polyamine demulsifier and preparation method and application thereof |
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| CN101352667A (en) * | 2007-07-26 | 2009-01-28 | 中国石油化工股份有限公司 | Demulsifying agent and preparation method and use thereof |
| CN101407730A (en) * | 2008-11-28 | 2009-04-15 | 句容市宁武化工有限公司 | Preparation of high performance demulsifying agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352667A (en) * | 2007-07-26 | 2009-01-28 | 中国石油化工股份有限公司 | Demulsifying agent and preparation method and use thereof |
| CN101407730A (en) * | 2008-11-28 | 2009-04-15 | 句容市宁武化工有限公司 | Preparation of high performance demulsifying agent |
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